Polymerizable acrylonitrile compositions and polymerization products thereof



UNITED STATES PATENT OFFICE POLYMERIZABLE ACRYLONITRILE COMPO- SITIONS AND POLYMERIZATION PROD- UGTS THEREOF Edward L. Krona, Old Greenwich, Conn., and Earl Malmberg, Dublin, Ohio, assignors to No Drawing. Application December 29, 1951, Serial No. 264,273

14 Claims. (01. 26047.5)

This invention relates to new and useful comdivalent aromatic hydrocarbon radical) containpositions of matter, and more particularly is ing from 1 to 7 carbon atoms, inclusive concerned with polymerizable and polymerized More specific classes of compounds embraced acrylonitrile compositions. Still more particuby Formula I are compounds of the following larly the present invention is directed to poly- 5 classes: merizable compositions comprising 1) acryloni- H CH3 Y CH, trile and (2) a compound represented by the J R, 7 g general formula I R Y on, 10 cm I ll m H Y CH1 CH1=CRZC N I I CH, oH,=oR'-z0-N I where R represents a member of the class co- IV R 0 3g sisting of hydrogen and the methyl radical, R I H represents a divalent hydrocarbon radical, Z OHz= -R-ZO-N I represents a member of the class consisting of oxygen and the imino (NH) radical, and Y V R s CH2 represents a member of the class consisting of A l r n oxygen and sulfur, the compound of (2) consti- CH2: I tuting from about 0.4% to about 35% by weight CH2 of the total amount of (1) and (2) and to prodv1 R Y CH2 ucts comprising such polymerized compositions, OH J! I a- C-N e g, a copolymer of copolymerizable ingredients including (1) acrylonitrile and (2) a compound CR1 or the kind embraced by Formula I in a weight v11 R Y 'CH: ratio of from about 1% to about 15% (more par- J R' NH-(L l latter, based on the weight of the total amount CH2 includes metlwd f l l whereby I16W and same meanings as given above with reference to radicals repres n d y R in the above formula ethylene carbamate, methallyl-N N-ethylene carare: divalent alipha c, t ethylene, propylene bamate, N-ally1-N,N'-ethyleneurea, N -allyll l m ylene), p penylene, butylene, isobutyl N'-ethylenethiourea, N-isopropenylphenyl-N, ene, pentylene, isopentylene, eta, including diethyleneurea, allyl-N,N-ethylene t iocarbamate,

pentenylene, etc. divalent aromatic, e. g., p enyethylenethiourea, N-vinylphenyl-N',N'-ethylenelene, xenylene, naphthylene, etc.; divalent aliph- 40 urea and N-vinyltolyl-N,N-ethylenethiourea. Mic-Substituted aromatic, o ,4-t y1ene, ethyl- Other examples will be apparent to those skilled 2 ,5-phenylene, isopropyl-3,4-phenylene, l-butylin the art from'Formulas I to VII, inclusive, and 2,4-naphthylene, etc. divalent aromatic-substifrom the definitions of R R, Z and Y appearing tuted aliphatic, e. g., phenylethylene, phenylin these formulas. propylene, naphthylisobutylene, xylylene, alphais one of the primary objects of the present (4-toly1ene) beta-buty1, etc.; radicals that may be invention to prepare a new class of copolymers classed either as divalent aliphatic-substituted for use in industry, for example in molding, aromatic 0r divalent aromatic-substituted aliphcasting, oati laminating and adhesive appliatic, e. g., 4,a1pha-tolylene, 3,beta-phenyleneetliyl, cations,

4,alpha-xylylene, 2,gamma-phenylenebuty1, etc. Another and important object of the invention Preferably R represents a divalent hydrocarbon is the production of new acrylonitri radical (e. g.,a divalent saturated aliphatic or a compositions which are more readily dyed, es-

with acid dyes, than liomopolymeric acrylonitrile or many of the copolymers of acrylonitrile and another monomer or monomers that were known or suggested prior to our invention. Another object of the invention is to prepare such copolymers which can be spun or otherwise shaped to form filaments, tapes, ribbons, rods, tubes, sheets, etc., and the shaped articles then dyed either before or after having been oriented to improve their useful properties.

Other objects of the invention will be apparent to those skilled in the art from the description and examples which follow.

These objects are accomplished, in general, by preparing a copolymer of copolymerizable ingredients comprising acrylonitrile and a compound (or a plurality of compounds) of the kind embraced by Formula I. The copolymer advantageously is produced, for instance, by" polymerizing, in a liquid medium in which the polymerizable ingredients are inert and with the aid of a polymerization catalyst (or catalysts), a mixture of comonomers including acrylonitrile and'on'e or more compounds of the kind covered by Formula I; and, at the end of the polymer"- ization period, isolating the resulting copolymer. The compound of the kind embraced by Formula I which is copolymerized with acrylonitrile in practicing our invention is employed in an amount corresponding to from 0.4 or 0.5% to 30 or 35%, preferably from about 1% to about by weight of the total amount of the said compound and acrylonitrile. The use oi higher proportions of the compound embraced by Formula I, for example 50% (or in some cases even as much as 75% of the said compound basedon the total weight of such compound and acrylonitrile, is not precluded but no particular advantages appear to accrue therefrom. In general, largely for economic reasons, no more of the ethyleneurea or ethylene carbamate compound should be employed as a comonomer with acrylonitrile than is required in order to obtain the desired results, for example improved dyeability, especially toward acid dyes.

Any suitable means may be used in effecting copolymerization of the acrylonitrile with the compound embraced by Formula 1. Heat, light, or both heat and light, with or without a polymerization catalyst, can be used. A polymerization catalyst preferably is employed in order to shorten the period of time required for polymerization of the mixture of ingredients comprising acrylonitrile and the cyclic ethylene? Any of the polymerization catalysts which are suitable for use in polymerizing compounds containing an ethylenically unsaturated: grouping, specifically a. vinyl grouping", be employed. Among such catalysts arethe inorganic peroxides, e. g., hydrogen peroxide, barium peroxide, magnesium peroxide, etc., and the various: organic peroxy catalysts, illustrative examples; of which latter are: the dialkyl peroxides, e. g, diethyl peroxide, dipropyl peroxide, dilauryl. peroxide, dioleyl peroxide, distearyl peroxide, di-ttert-butyli peroxide and d1.- (tert.-amyl) peroxide, such peroxides often be ing designated as ethyl, propyl, Iauryl 'oleyl, stearyLtert-butyl and tort-amyliv peroxides; the alkyl hydrogen peroxides, e. g., tert-.-butyl hydrogen peroxide (tort-butylhydroperoxidel, tert.amyl hydrogen peroxide (tert.-amyl hydro peroxide)", et'c.; symmetrical diacyl peroxides, for instance peroxides which commonly are known under such names as ace'yl peroxide,

pecially propinoyl peroxide, lauroyl peroxide, stearoyl peroxide, malonyl peroxide, succinyl peroxide, phthaloyl peroxide, benzoyl peroxide, etc.; fatty oil acid peroxides, e g., coconut oil acid peroxides, etc.; unsymmetrical or mixed diacyl peroxides, e. g., acetyl benzoyl peroxide, propionyl benzoyl peroxide, etc; terpene oxides, e. g., asc'aridole, etc.; and salts of inorganic per-acids, e. g., ammonimum persulfate, sodium persulfate, potassium persulfate, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, sodium perphosphate, potassium perphosphate, etc. Other examples of organic peroxide catalysts that can be employed are the following:

Tetralin hydroperoxide tert.-butyl diperphthalate Cumene hydroperoxide tert.-butyl perbenzoate 2,4-dichlorobenzoyl peroxide Urea peroxide Caprylyl peroxide p-clhlorobenzoyl peroxide 2,2i-bis-(tert-butyl peroxy) butane Hydr'oxyheptyl peroxide Diperoxide of. benzaldehyde Other so-called free radical types of catalysts, e. g'., -azodiisobutyronitrile, also can be used to accelerate polymerization.

If desired, the mixture of monomers can be polymerized in. emulsion or in yield a copolymer. Good results are obtained by effecting copclymerization while the monomers are dissolved in a suitable solvent, e. g,

aqueous alcohol, benzene, toluene, xylene, etc. Preferably the copolymerizationreaction is carried out in a liquid medium inwhich the mono-- meric mixture is solublebut the copolymer is insoluble.

The polymerization also can be effected by conventional bull: polymerization technique, in the presence or absence of a solvent capable of dissolving the monomeric mixture and in which the latter preferably is inert; or by conventional bead polymerization methods. The polymerization of the mixture of monomerscan be effected by a continuous process as well as by a batch operation.

The concentration of the small, e: g., from, by weight, about 1 part of catalyst per 1000 parts of the monomeric mix-- hire to about 3 or 4- parts of catalyst per parts of the mixture of monomers.

The temperature of polymerization of the polymerizable composition comprising acryloni trile proportions specified in the first paragraph of this specification can bevaried over a wide range, up toand including or slightly above the (at atmospheric pressure) of the monomeric mixture. In most cases, the polymerization temperature will be within the range of about 20?" or" 30 or' 40 C., up to the boiling temperature or the mixture of monomers, depending, upon the particular catalyst, if" any, rapidity of polymerization wanted and other influencing factors". The use of polymerization temperatures substantially above the boiling point or the mixture of monomers is not precluded, but generally is less desirable because the polymerization reaction then must either be carried out in a closed reaction vessel under pressure, or, for economical reasons, with a resolution state to catalyst is relatively and the cyclic ethylene compound in the C., preferably at least 35 v for example;

used, the

586,881 with reference to the production of other polymerization products. The copolymers of ingredients comprising combined acrylonitrile and If the copolymerization reaction is carried out while the mixed monomers by any suitable means, e. g. fuging, solvent extraction, etc.

EXAMPLE 1 Preparation of N-aZlyl-N,N'-ethyleneurea solution and for one hour and fifty minutes there- N-allyl-N',N'-ethyleneurea separates out as a cloudy oil which becomes clear on standing and can be separated from the hexane.

EXAMPLE 2 Preparation of N-allyl-N,N-ethylenethiourea Separation of the lower layer gives 71.8 g. (a quantitative yield) of N-allyl-N,N'-ethylenethiourea as an orangecolored oil.

The above reaction can following equation: vrrr cm om=o HCH;NH( -N l Hz EXAMPLE 3 Prepwration of allyl-N,N-ethylene carbamate A solution of 60.2 g. (0.5 mole) of allyl chlorocarbonate dissolved in 200 ml. of benzene, which solution is at a temp rature of 4-5 of 83-86 C. cury. It is 78.9% of the The above reaction can following equation wherein "'IEA represents triethylamine. IX 0 CH:

TEA CH=CH-CH1-O- -o1+ HN H 0 OH: I; CH:=CHCH:-O N TEAIIC] CH: EXAMPLE 4 Prepamation of N-isopropenylphenyZ-N',N- ethyleneurea A solution of 19 g. of ethyleneimine dissolved N-isopropenylphenyl-N', '-ethyleneurea 1s filtered ofi, washed first with about 45 g. of benwhich it is allowed to air-dry for The yield is quantitative (79 g.).

The above reaction can be illustrated by the following equation: X

H O CH:

OH: OH,

HN l H: =02! o=oH, H1 $11: In order that those skilled in the art may better be illustrated by the be illustrated by the areagiven byway-pt' illustraition? and not byl way of limitation. All parts and percentages-remap}; weight.

EXAMPLE 5 This example illustrates the preparation of homopolymeric acrylonitrile, which is subsequentlyemployed in comparative tests with certain of the copolymers of the present invention.

A reaction vessel, equipped with a stirrer, reflux condenser, thermometer and gas-inlet tube, is placedima.constant temperature bath which is maintained at 35 C. To the vessel is added a solution or 53.0, partsof 'acryloni'trileflloo parts oddistilldwvater aridoz29 part" or sulfuric-acid. The 'pi-I' of the initial" solution is' 3.1. A rapid stream or pre=purifiednitrogen is passed over the surface or the solution for 30 minutes. The nitrogen flow is then reduced toabout one bubble p'ersee'ond. reduction-oxidation catalyst sys- V tem ("redox' system) consisting oflfll parts'of ammonium" persulf'ate' and 071 part or sodium meta bisulfiteyeach dissolved in 50 parts of water, is then added. The solution first'be'comes cloudy at the end'o'f 3 minutes, and the polymerization isiairly exothermic for the first half hour. The polymerization 'is continued for a total of 4; hours at'35'C. The polymer is'collected on a-Biichner iunrrelr-and washed" with looo'parts of distilled water followedby' about 160 "parts-of methanol. The polym'er is dried in an oven at 70 C. for about 16 hours. The yield -or dry polyacrylonitrile, which is white; amounts'to 48"parts.

EXAMPLE 6 This example. illustrates the production of a copolymer of acrylon'itrile andt-allyl -N ,Neethylene carbamate.

Fifteen (15). g. of acrylonitrile is placed in a Z-necked reaction vessel to which is then added TO- 80 mgrof allyl-NpN-e hylene "carb'amate, followed by 300ml. of water in small portions with intermittent stirring. intermittent stirring is continued and. ma .short. period a single phase results. Nitrogen gasispassed over the surface of the solution, and there is then added a solution o'f' i23" g. eisod'ium meta-bisulfite dissolved in 8 mlyoi water and a solution-oi- 0.6g; of potas= sium persul-fate dissolved in l?- ml.-of water. "The reaction mass is'stirred while maintaining it'at a-temp'erature of 30 -33 0., and in a short period copolymerizat-ion begins as evidenced by coagulation of the' mixe'd monomers. Stirring and heatbag are continued for a total of 2' hours, at the end of which periodthe coagulated copolymer isfiltered o'fi washed first-with water and then'with methanol, a-iter Whichthe filter cake is compressed-andallowedto dryfirst in air and' then in a"70"C.' oven to a constant weight. The resulting copolymer is testedior its dyeability as describedin a later example.

EXAMPLE '7 This example illustrates the preparation of a copolymer of acrylonitrile and N-isopropenylphenyl-N' ,N -ethyleneurea.

Parts N Isopropenylphenyl N',N'- ethyleneurea .2 Acrylonitrile '30.0 Ethyl alcohol 120.0 Water i T 400.0 Sodium meta-bisulfite r .154 Potassium 'persul-iate a .4

1 Phebe-atedissolved-m n total of 50139.11! 01 water.

scribedunder Example 7' with soft gel. Upon further i lihermixtu'r'er of theabove ingredients isstirred at50 zzioria total of 5 hours at the end ofwhich periodia .copoly'rner or. thet-sacrylonitrile with: the cyclic? ethylene compound has formed. The 00- polymer is filtered off, washed with water: and then- 'withmethanol. Thereafter it is dried first iniair and'theniin a"l0 C. oven to a constant weight. The yie'ldoi copolymer is 76% of the theoretical. .It. is tested for its dyeability as described in a l'ater example.

"EXAMPLE 8 This example illustrates the preparation 'ofza copolymer r-of aerylonitrile and N-allyl-NQN ethyleneurea.

Parts N-allyl' NflN'-ethyleneurea 0.24 Acrylonitrile 30.0 Water r r 600.0 sodium meta-bisulfite .922 Potassium persulfate A 2.4

a total of 50 parts of water.

is: followed as de the exception that the time:of:po1ymerization is about '7 hours and ther drying is. carried-"out for about 16 hours at room temperature andthe-n in a c oven' to a constant Weight. The yieldof copolymer Of acryis about 83% oi' thetheoretical. it is tested: forits use ability as? described in th'e'next example.

Samplessof the 'homo'polymeric acrylonltrile of Example 5 and of thecopolymers of Examples 6, '7 and 8 are subjected to the following dye test: A 'sampleidparts) :of the dryflpolyiner or copolymer v is added to a dye bath consisting of 500 parts of an aqueous solution. containing 0.2 part of.concentratedsulfuric acid, 1 part of sodium sulfate varid.0.2 part of Calcocid Alizarine Blue SAPG (Color Index No. 1054). The dye bath is boiled for30. minutes, after which the-polymerization product isfiltered off and washed With hot water until 'the water is free of dye. Thecopolymers of -Examples cgv and .8 are dyed blue, Whereas, the homopolymeric acrylonitrile oLExample -5'iails to absorb any dye. The advantage of modifying v.an acrylonitrile polymerization product by replacing a part, moreparticularly from about 0.4%.to about 30 or 35% or more, and specifically'from 1 or 2% to 10 or 15% of the initial acrylonitrile, with a compound of the kind embraced by Formula 1, thereby to obtain a copolymeric acrylonitrile substance of improved dyeability, is therefore quite apparent.

1 These are dissolved in :Exactly: the same procedure EKXANIPLE-1O Parts Acrylonitrile 90 N=Isopropenylphenyl N",N'-ethyleneurea 10 are heated together on a steam bath underanhydrous reflux. conditions yielding a copolymer of theabove comonomers.

yield a clear: solution after heating together for a brief period. Upon heating on a steam bath for about 30 minutes, the solution polymerizesto a heating the copolymer oi ardens, and at the clear reddish-brown material.

EXAMPLE 12 Parts Ethyl acrylate 70.0 Acrylonitrile 20.0 N-Isopropenylphenyl-N,N-ethyleneurea 10.0 Alpha,alpha-bis-azoisobutyronitrile .5 Toluene 50.0 The solution of the above ingredients is heated in a closed reaction vessel placed in a boiling sulfate and sodium bisulfite as a redox catalyst system and carrying out the polymerization reaction in aqueous ethanol solution.

In a typical embodiment of the ployed in this phenyl-N',N'-ethyleneurea is dissolved in 75 ml. of ethanol and bisulfite in 10 ml. and 0.60 g. of potassium persulfate in water are added in that order.

stirred and kept at a temperature 15 ml. of The mixture is C. for

to g. of acrylo 1y 25% aqueous ethanol TABLE I Wt. ratio IPPE UzAN In Table I the abbreviation IPPE U" means N lsopropenylphenyl N',N' ethyleneurea and AN means acrylonitrile. clfic viscosity the copolymer dissolved in 100 ml. of a aqueous solution of sodium thiocyanate.

EXAMPLE 14 This example illustrates the polymers of phenyl-N',N'-ethyleneurea by solution polymerization and results The abbreviations same meanings as Table I.

TAB LE II AN in are tabulated in Table II. IPPEU and AN given above with reference to Wt. ratio 'Iemp., Catalyst, g/

IPPEU:AN o o. g./I. l f Results soln.

1:56 2.0 56 Started to copolymerlze after 1 hr.; 10W

1:48 65 2.0 48 Cllipsoily merized after 1:40 .i 65 2.0 40 Solid oopolymer when r moved after 2.5

hrs.

EXAMPLE 15 This example illustrates the production of copolymers of acrylonitrile and allyl-N,N-ethylene TABLE III Weight ratio of allyl-N, Nfgetlhylene carbamate to acry- Yield in om r e 1 percent 1: 188 1 o EXAMPLE 1 6 This example illustrates the preparation of of acrylonitrile and Nallyl-N',N'- ethyleneurea. The procedure is essentially the polymerization conditions and the results obtained are given TABLE IV Cone. of monomers g. per liter Wt. ratio In Table IV the abbreviaton AEU means N-allyl-N',N-ethyleneurea and AN means acryl'onitrile.

EXAM-P1114! Parts Acrylonitrile 9 .9 N-allyl-N,N-ethyleneurea .53 Methyl aerylateu n'l 2.65 Water 900.00 6 N sulfuric acid"; .7 Ammonium persulfate in 50 parts of water Q. 1.71 Sodium meta-bisulfite in 5 0 parts of water. .36

A reaction vessel, equipped with a stirrer, rex conden er ermomete nd esame? tube is placed in a water bath maintained at a temperature of 30-35 C. Asolution of all of the above ingredients, with the exception of the acrylonitrile, methyl acrylate, ammonium persulfate and sodium 'meta tbi ulfite, is added to the reaction vessel; A rapid stream of pro-purified nitrogen is passed over the surfaceflof' the solution for 30 minutes, The nitrogen' flow is then reduced to one bubble perl second, The remaining ingredients are, 'dded, and the. re; action is allowedto. proceed atfabout while continuing the stirring, for a total of about 6 hours. Theresulting copoly'rner oi acrylqni; trile, methyl aorylate an N-ally1 -N',N-ethyl-, eneurea is collectedon'a Biichneriunnel, washed with 2000 parts or deie'riizejf Waterman dried in an ovenat 70 C(foifihbclht l6fhours. This copolymer is suitable'ioruse' in cproduction of a especially a similar which fiber having improved'dy'e' receptivity, toward acid dyes, as compared with acrylonitrile-methyl acrylat'e copolymer in no N-allyl-N,N-ethyleneurea is present.

It will be understood, of course, by those skilled in the art that our invent dnlfis not. l mitedtqfihs specific, ingredients named in the above illustra; tive examples nor. to. the, particular proportions and methods. of eopolymerizationw lmentioned therein. Thus, instead of the particular catalyst or reduction-oxidation ire dox) catalyst system named in the difierent examples, any other polymerization catalyst or combination of, polymerization catalysts, numerous exampleszoi, which have been given. hereinbefore, can beused.

Likewise, other modifying. comonomers in addition to the ethyl acrylate named inExample 12 and the methyl acrylate of Example 1'7, can be used. Illustrative examples of such cornonorners are vinyl compounds which are difierent from acrylonitrile (vinyl cyanide), including the vinyl aromatic compounds, more particularly the vinyl aromatic hydrocarbons (e. g., styrene, isopropen- Yield, percent yltoluene, the various diallgyl styrenes, etc) other aliphatic compounds containing a Clix- 1514 grouping, e. g., theyarious substituted acrylo; nitriles (e'. g., methacrylonitrile, etha orylonitrile, phenylacrylonitr ile, etc.) acrylamide, an ql the various substituted acrylamides (e g., meth y m d r e haq y amide, h va i us 7 132: stituted acrylamides: and the variousN-substi;

tuted se r amldes for tance N methvlq acrylamide, N-monoalkyl and -dia lkyl acryl: amides and methacrylamides, e. g., N monomethyl, -ethyl, -propyl, -butyl, etc., and N-dimethyl, -ethyl, -propyl, -butyl, etc., acrylamides and methacrylamides, Nemonoaryhand -.diaryl acrylamides and alkacrylamides, .e. g., N emonophenyland l-diphenyl acrylamides randlrneth acrylamides, etc), vinyl. esters, erg" vinyl, ace; tate, vinyl propionate,-.. vinylzbutyrata. vinyl isobutyrate, vinyl valerate, ivi-nyl acrylate-, vinyl methacrylate, etc, esters. ofan acrylic acid, more particularly, the alkylesters oi acrylic'faoid, eg.. h e hyl pr pyl, i p qnyl, nebutyl, isobut: v um, tertebntyl, amy hexylr heptyl, 0c y1-, y1,. dodecyl etc, esters. of cryl c.- aci cludingthe, lkyl a rylat s ontaining not, m e han i uri arb n. atomsin th alkyl roup; ns exa ples. of hi e iv n -.a ve as wel a ot er vinyl a o atic and vinyl a phat come oun s n r; om unds e onta n nsaa CH1FC o p n l ore arti ul rly as n le z .C u i g.

he, opor ions o ny, iod i-vinsomonemer r mo ome hat re corpor ted. the pql mer able om osit on: to ether; w th th n tri e nd e cli -l e ylen o e s ml ith n e h acedrbr Formal-c n h ir desired r; s; r ar rh r n hees, 349, 1 r p en ndera PIPPOlTF O k m re-f ten ,b ieh. 5: t e qtalr s eht more? rs l mslie s ,o her r l she l r ersz 922 nd ons es from... bou Oito; bo t 35% mQre. particu rly m 1 91 we 29:Qr12 %l-Qfi.. het el ..eishtoi-thee. ni ri nd c ic th enem m nsi. and. an q if yinscomonemer or-rc mpnqms (i ipre nt athe l e iea lemixte a uar m-th s t i mon mers h i o al; me

s e iea n on it rs m new ticularly thermoplastic ee ioiyrnei'ee l of the present invention,-the acrylonitrile is employed in the mixture of comonomers in an amount such thatat-least byweight oi combined. acrylonitrile ispresent 'in the copolyrner.

Although the new-.copolymers of this invention are particularly useful in the formation of fibers or filaments which are more amenable-to dyeing, than homopolymeric acrylonitrile, they also have numerous other applications-in -the" plastics and coating arts. For instance, with or tures of the order of 130 C. or 140 C. to 200 and under pressures up to 10,000 pounds or more otherwise treated.

The present invention copolymer compositions in which a cyclic ethyl- Since the copolymers of the inven tion, and fibers produced therefrom, are amenable to animalization, as by the introduction of amine groups, animalized" products can be produced that are readily and deeply dyed with dyes such as are used in dyeing wool, e. g., acid dyes.

We claim:

1. A polymerizable composition comprising (1) acrylonitrile and (2) a compound represented by the general formula where R represents a member of the class consisting of hydrogen and the methyl radical, R

by weight of the total wherein Z repcopolymerizable ingredients including (1) acrylonitrile and (2) a compound represented by the general formula where R represents a member of the class consisting of hydrogen and the methyl radical, R represents a divalent of (2) constituting from about 1% to about 15% by weight 01' the total amount of (1) and 2).

8. A composition comprising a copolymer as in claim 7 wherein R represents a divalent aliphatic hydrocarbon radical.

9. A composition comprising a copolymer as in claim 7 wherein R represents a divalent aromatic hydrocarbon radical.

10. A composition comprising a copolymer of copolymerizable ingredients including (1) acrylonitrile and (2) allyl-N,N-ethylene carbamate, the compound of (2) constituting from about 1% to about 15% by weight of the total amount of (1) and (2).

11. A composition comprising a copolymer of copolymerizable ingredients including (1) acrylonitrile and (2) N-allyl-N',N'-ethyleneurea, the compound of (2) constituting from about 1% to about 15% by weight of the total amount of (1) and (2).

12. A composition comprising a copolymer of copolymerizable ingredients including (1) acrylonitrile and (2) N-allyl-N,N'-ethylenethiourea, e compound of (2) constituting from about to about 15% by weight of the total amount of (1) and (2).

3. A composition comprising a copolymer of copolymerizable ingredients including (1) acrylonitrile and N-isopropenylphenyl-N',N'- ethyleneurea, the compound of (2) constituting from about 1% to about 15% by weight of the total amount of (1) and (2) where R represents a member of the class consisting of hydrogen and the methyl radical, R

rehmsfintx a2. divalentfihydmeanba'xiradical,; Z represents a. member of.the :classzconsistmggaof oxygen: anda'the: imino; radicah. and :Y::rep1tesents a member of the class consistinggui: oxygenrand about 0.4% to about 35% by weightz'ot" thertotal amount. of 1(1) l and; (2):, iand=wismating@.the.;re-

sulting copolymer from the saidliquimmed'mm.

V EDWARDZLKRQPA;

M-AL-IVI ERG .rv

sulfur, .thezacompeun 01 .(2): constituting. from a Rmrmces 1Cite' STATES 'P Number.

Namey Caldwell;

Date 13,1951 

1. A POLYMERIZABLE COMPOSITION COMPRISING (1) ACRYLONITRILE AND (2) A COMPOUND REPRESENTED BY THE GENERAL FORMULA 